Electrical Loss Management by Molecularly Manipulating Dopant‐free Poly(3‐hexylthiophene) towards 16.93 % CsPbI2Br Solar Cells.

Inorganic cesium lead halide perovskites offer a pathway towards thermally stable photovoltaics. However, moisture‐induced phase degradation restricts the application of hole transport layers (HTLs) with hygroscopic dopants. Dopant‐free HTLs fail to realize efficient photovoltaics due to severe electrical loss. Herein, we developed an electrical loss management strategy by manipulating poly(3‐hexylthiophene) with a small molecule, i.e., SMe‐TATPyr. The developed P3HT/SMe‐TATPyr HTL shows a three‐time increase of carrier mobility owing to breaking the long‐range ordering of "edge‐on" P3HT and inducing the formation of "face‐on" clusters, over 50 % decrease of the perovskite surface defect density, and a reduced voltage loss at the perovskite/HTL interface because of favorable energy level alignment. The CsPbI2Br perovskite solar cell demonstrates a record‐high efficiency of 16.93 % for dopant‐free HTL, and superior moisture and thermal stability by maintaining 96 % efficiency at low‐humidity condition (10–25 % R. H.) for 1500 hours and over 95 % efficiency after annealing at 85 °C for 1000 hours. [ABSTRACT FROM AUTHOR]